Note: Descriptions are shown in the official language in which they were submitted.
i07 11855-C-1
BACICGRO~'ND OF THE IN\'E~TIOI~
Governmental reg~lations have plaeed ever
increasing restrictions on the amounts and eypes of
os~,anic volatiles permitted to escape into the st s-
phere from coating compositions. Considerable efforts
have been expended to develop coatings compositions
having a mi nimal ~mount of volatile organic components
and this hss led to the development of powder coatings,
radiation-curable coatings, and water-borne coatings.
Yigh solids coatings represent another ~ttractive
technology to reduce solvent emissions. In ~hese re-
cen~ developments, the amounts of organic solvents
present are minimal ~nd consquently there is little
or no atmospheric pollution.
A compound often used in the production
of coating and ink formulations is 2,2-dimethyl-
3-hydroxypropyl 2,2-dimethyi-3-hydroxypropionate
(also known as ED-204). ~owever, the ~ormally solid
~ature of ED-204 and other ester ~iol5 has on occasion
~0 presented some problem~ in use. It has been recently
discovered that ester diols can be reacted with al~ylene
o~ides to form liquit vehicles which, depending upon the
particular alkylene oxide selected~ can be either water
soluble or w~ter insoluble; these have been called ester
di~l alkoxylates. ~ny further discoveries that would
al90 serve to lower atmospheric pollution would be of
interest for use in industry.
)7
11855-C-l
S~S~RY OF THE Il~.~ION
It has now been found that certain deriva-
tives of the ester diol elkoxylates can be produced
- thst are useful in the production of coating and ink
formulations. Ihese derivatives are obtained by re-
acting an ester diol alkoxyla~e with an intramolecular
polycarboxylic acid anhydride, or an organic poly-
isocyanate, or a polyepo~ide, or combinations thereof.
The resulting products have been found useful in the
production of high solids compositions. These high
solids compositions additionally contain cross-
linkers and can contain pigment, solvents, flow control
agent, plus any of the other additives conventionally
present in a coating or ink. They can ~lso be blended with
other polymers and latexes to yield compssitions that pro~
duce dry films having accepta~le proper~ies.
D ~ ~]~
The ester diol alk~xylate derivatives, as
well as the ester diol alko~ylates themselves, and
the methods for their production ~re discussed in de-
tail below.
The Ester Diol Alko~Ylates II
~ he ester dioL alko~ylates belong ~o a new
class of ~terials ~ust recently discovered and the
subject matter of a different application. These ester
diol alkoxylates are psoduced by the reaction of an
es~er diol of the structural formula:
11855-C-l
R R
1. HOCnH2nCcn~2nOocccnH2noH
R R
with an oxirane co~pound, preferably an alkylene oxide,
to produce the ester diol alkoxvlate of the structural
formula:
R R
II. H(OCmH2m)xOCnH2nCCnH2nOOCCCnH2nO(C2H2~0)yH
R R
wherein m is an integer having a value of from 2 to 4,
preferably 2 or 3; n is an integer having a value of from
1 to 5, preferably 1 to 3 and nost preferably 1; x and y
are integers each having a value of from 1 to 20, preferably
1 to 10; R is an unsubstituted or substituted, linear
or branrhed alkyl group having from 1 to 8 carbon ato~s,
preferably 1 to 3 carbon atons. The subseituents on the
R group can be any inert group that will not interfere with
the reaceions involved and can be, for example, cyano,
halogen, alkoxyl, nitro~ tertiary amine, sulfo, etc. In
the formulas, the variables R, m, n, x and y ca~ be the
same or different at the various locations.
The novel est~r diol alkoxylates (II) are pre-
ferably produced by the catalytic reaction of an ester
diol ~I) with an alkylene oxide or mixtures of alkylene
o~ites at an elevated te~perature as more fully discus-
sed below. One can ~anufaceure the mono, mixed, bloc~ed
or capped adducts.
~ 7 11~55-C 1
The alkylene oxides suitable for use in the
produotion of the ester diol alkoxylates sre the oxirane
com~ounds such ~s styrene oxide, ethylene oxide, 1,2-pro-
pylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, ~
1,3-butylene oxide and 1,4-butylene oxide as well as
similar higher aliphatic noepoxides.
The ester diols of ~orm~la I include 2,2-di-
methyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate;
2,2-dimethyl-4-hydroxybutyl 2,2-dimethyl-3-hydroxypro-
pionate; 2,2-dimethyl-4-hydroxybutyl 2,2-dimethyl-4-hy-
droxyb~tyrate; 2,2-dipropyl-3-hydroxypropyl 2,2-dipropyl-
3-hydroxypropionate; 2-ethyl-2 butyl-3-hydroxypropyl
2-ethyl-2-butyl-3-hydroxypropionate; 2-ethyl-2-~ethvl-3_
hydroxyprowL 2-ethyl-2-methyl-3-hydroxypropionat~;
and the like.
Dur~ng the reaction of the ester diol I with
the alkylene oxide a catalyst is preferably used in a
catalytically effective amount. Ihe amount of catalyst
is fr~m 0.01 to 5 weight percent, prefera~ly from O.OS
tQ 0.5 we~ght percent, based on the combined weights of
ester diol I and alkylene G~ide. The cstalysts useful
are known to those skilled in the art of alkylene oxide
addition chemistry and require little further discussion
here. Illustrative thereof one c~n mention boron tri-
fluoride etherate, potassium~ potassium hydroxide, sodi
sodium hydroxide, Lewis ~cids, sodi~m ethoxide, mineral
acids, and the like.
il;~'~ti()7
11855-C-l
The re~ction of the ester tiol with the
slkylene oxide is carried out at a temperature of from
20 to 150C, preferably from 50 to 120~C. for a period
of time sufficient to complete the reaction between the
- reactants char~ed. The temperature is often dependent
upon the particular catalyst selected and the alkylene
oxide em~loyed. ~he time will vary depending upon ehe
size of the batch and the particular reactants ~nd cat-
alyst~ and the rea~tion conditions employed.
The reaction can be conducted at subatmospheric,
~tmospheric or superat spheric pressure. The pressure is
not critical and sufficient pressure is generally used to
retain the reactants in the reactor in liquid form.
The a unt of alky~ene oxide charged to the re-
action i9 from about 2 les to about 40 les, or re,
per mole of ester diol charged; preferably from 2 to 20
~oles.
To minimize oxidative side reactions the re-
action ~s preferably carried out under an inert ~s at-
~DspherP using nitrogen, argon or other inert gas.
If desired an inert solvent such as toluene, ben-
ze~e or l,l,l-trichloroethane can be employed. However,
~he reaction proceeds well in the absence of any such sol-
vent. In most ~nstances a solvent is not required as the
ester diol is itself a liquid at the elevated temperatures
employed and serYes ~o maintain a liquid reaction system.
At the conclusion of the reaction the product,
consisting of a mixture ~f the novel ester diol
ll'h'~C~7
ll8 j5-C -
alkoxylates, is recovered as ~ residue pr~duct and can
be used 85 such; distillation pr~cedures ca~ ~lso be
used to recover more refined products.
The ester diol alkoxyl~tes can be used as
_ ~olvents, vehicles in paint or ink formulations, water-
bosne coatings, as an intermediate in the production
of other valuable c~mpounds and as a ~urfactant as well
as i~ producing the derivatives of this invention.
In a typical ~mbod;~nt, the ester diol and
catalyst are charged to the reactor and the alkylene
oxite is then ~dded over a period of time while main-
taining the desired temperature and pressure. At the
com~letion of the addîtion the c~ntents of the reactor
are maintained at the selected eonditions until substan-
tially all of the alkylene o~ide has reacted. The produc~
can then be purified, if desired, ~nd recovered by con-
venti~nal proceduresO In SQme instances one m~y obtain
a product containing other glycols as by-products. This
can be ~ nimized by proper selection of reaction conditions
and catalyst.
The Anhydride Modified Ester Diol Alkoxvlates III
~ he catalytic reaction of the ester diol alkoxy-
lates of formula II with an intramoleculas polycar~oxylic
acid anhydride produces ~ derivative that contains ~ree
carboxyl groups. This oan be illustrated by ~he following
formula, in which phthalic anhydride is ~mrloyed for il-
lustrative purposes, that shows the resultant product
i07
11855-C-l
~OOH F~
~ COO~ 03C ~
obtained by the re~ction of two mDles of phthalic
~ snhydride per le of ester diol ~lkoxylate II.
Illustrative ~f suitable polycarbo~ylic
acid anhydrides that can be used one can mention
trimellitic ~nhydride, tetrahydrophthalic anhydride,
~hthalic anhydri~e, benzophenone dicarbo~ylic ~cid
anhydride, succinic anhydride, maleic aDhydride,
lD ~aphthoic anhydrite, ~lutaric ~nhydride, or any other
intramolecular anhydride, including those having sub-
stituents thereon such as halogen atoms, alkyl or
alkoxy groups, ~itro? carbo~yl,aryl, or any other
- group which will not unduly interfere with ~he reaction.
The ~m~un~ of polycarboxylic acid anhydride
re cted with ~he ~6ter diol alkoxylate II ca~ be an
Emount sufficient to permit reaction with all of the
hydroxy groups; however, it ~s preferred to use ~n
a~ntwhich ~s insufficient to re~ct with all of the
hydroxy roups present in the ester diol alkoxylate II
or derivative there3f. This ~mount will vary and can be
from 0.1 to 1 anhydride equivalent for cach hydroxyl
equivalen~ or group present in the ester diol Alko~y-
late II initially charged to the reaction mixture ~nd
is preferably from 0.1 to 0.6. In a m~st preferred in-
sta~ce, ~ne anhydride equival~nt ar anhydride moiety
~ 7 118~5~
is charged for each hydroxyl equivalent or group ln-
itially present in the reaction mixture. I~ ~he
react~on a conventional esterification catalvst can be
used. Ihese are well known to ~hose skilled in the
art.
The ester diol ~lkoxylate II is reacted with
the polycarboxylic acid slihydride at a temperature of
from about 75 to 200C, preferably from about 100C to
150C. The time required for reaction will vary depend-
ing upon the particular reactants charged, the temperature,and the batch size of the reaction mixture, facts which
are ~ell known to those skilled ~n the art. Generally9
it has been found th~t a reaction period in the Labora-
tory of from 15 to 6Q minutes at from 125 to 150C is
adequate to produce the initial carboY,yl-modified ad-
dition reaction pr~duct obtained by the reaction Or these
two intermediates.
The anhydride modified ester diol alkoxylate
III of this reaction is a viscous liquid, in st in-
stances. However, in some instances it has been observedthat the product will solidify upon standing at room tem-
perature for gn extended period of time. miS, however,
does ~ot detract from its ~ur~her utility. Generally,
these modified adducts are soluble in both wster and
solvents.
e Isocyanate Modified Ester Diol Alkoxylates IV
The c~talytic reaction of the ester diol
alkoxyl&tes II with a polyisocyanate produces a hydroxyl
Z~ 7 11855-c-
ter~inated de~ivative that contains urethane gr~ups IV.
This can be illustraeed by the following equation, in
which OC~ CO represents 8 diisocyanate, and shows the
reaction of 2 moles of II with one mole of a diisocya-
nate: O
2 II ~ OCNXNCO ?II-OCNHXHNCO-II
(IV)
The polyisocyanates that C&n be used in this
invention ~re well known to those skilled in the art and
~hould not require detailed description herein. Any of
the polyisocyan tes c~n be used alone or in admixture
with other isocyanates including the noisocyanates.
Illustrative thereof one can mention methyl isocyanate,
ethyl isocyanate, chloroèthyl isocyanate, chloropropyl
i~ocyanate, chlorohexyl isocyanate, chlorobutoxypropyl
isocyanate, hexylisocyanate, phenyl isocyanate, the o-,
m-, and p-chlorophenyl isocyanates, benzyl isocyana~e,
~aphthyl i~ocyan~te, o-ethylphenyl isocyanzte, the di-
chlorophenyl isocyanates, butyl isocyanate, n-propyl
isocyanate, octadecyl isocyanate, 3,5,5,-trimethyl-l-
isocyanato-3-isocyanatomethylcyclohexane, di(2-isocya-
natoethyl)-bicyclo-(2-2-1)-hePt-5-ene~3-dicarboxylate~
2,4-tolylene diisocyanate, 2,6-to~ylene diisocyanate,
4,4'-diphenylmethane diisocyanate, dianisidine diiso-
cya~ate, tolidine diisocyanate, hexamethylene diisocya-
~ate, dicy~lohexyl-4,4'-methane dii~ocyanate, cyclohex2ne-
1,4-diisocyanat~, 1,5-naphthylene diisocyanate, 434~-diiso-
cy~nato diphenyl ether, 2,4,6-triisocyanatotoluene, 4,4',
10 .
07
1185~ -C-l
4"-triisocyanato ~riphenyl ~e.hane, di?henylene-4,4-diiso-
cyanate, the polymethylene pol~?henylisocya~ates as well
as sny of the other organic isocyar.ates known t~ the
average skilled chemist.
The ~mount of ester diol alkoxylate II used can
- be an a~ount sufficient to permit reaction of the
isocvanato ~roup with up to about 0.9 equivalent to the
total number of hydroxyl groups present. Thus, fro~ 0.025
to 0.9 isocyanato equivalent is reacted pe~ hydroxyl
10 equivalent, preferably from 0.04 to 0.5 isocyanato equi~alent
per hydroxyl equivalent, and most preferably from 0.04 to
0.25 isocyanato equivalent per hydroxyl equi~alent initially
charged. The conventional urethanP reaction catalvsts are
used.
The reaction of ester diol alkoxylate II with
isocyanate is conducted at a temperature of fro~ about 25C
to 100C preferably from about 40C to 60C. The time
required will vary depending upon the particular reactants
char~ed, catalyst, te~perature, and the batch size of the
2~ reaction mixture, facts ~hich are well known to those
~killed in the art. Generallv, it has been found that a
reaction period of from 1 to 5 hours at from about 40 to
60C, is adequate to produce the urethane-mGdified product.
This product IY can be used per se or it can be capped
or modified with a carboxylic acid anhydride by the
reaction o~ this hydroxyl terminated isocyanate
modified ester diol alkoxylate IV with an intramolecular
carboxylic acid anhydride by the same procedure~ here-
inbefore described for producing the anhydride modified
~ Z~07 11855 ~-1
ester diol alkoxylates III. In this instance the com-
pounds produced can be represented by the general
schematic formula:
IV A
COOH O COOH
- b--COO~ OCNHX`lHCO-II-OOC ~
which shows the product obtained by the reaction of
IV with phthalic ~nhydride when fully capped.
The EPoxide Modified Ester Diol Alkoxylate~ V
The catalytic reaction of the ester diol
alko~ylate II with a diepoxide Plso produces a hy-
droxyl terminated derivative. This can be illustra-
ted by the following equation in which two moles of
II react with one mDle of a diepoxide ~o prod~ce V:
2 TI + ~ ~ V ~
~1 ~
II ~ O . ~ O - II (V)
OH OH
in which,~
~~ ~V
2~ represents a diepoxide.
12 .
11855 - C-2
The diepoxides that can be used in this
invention are well Icnown to those skilled in the
art and are fully described in U.S. Patents 3,027,
357; 3,890,194; and 2,890,197. Of particular in-
terest is that portion of U.S. 3,027,357 begin-
ning at column 4, line 11 to column 7, line 3B.
Among some of the specific illustrative diepoxides
disclosed herein one can mention 3,4-epoxycyclohexyl-
methyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxy-
6-methylcy~lohexylmethyl) adipate, bis(2,3-epoxycyclo-
pentyl? ether, vinyl cyclohexene dioxide, 2-(3,4-epoxy-
cyclohexyl~-5,5-spiro-(2,3-epoxycyclohexane)-m-dioxaneJ
bis~3,4-epoxycyclohexylme~hyl)adipate, and the like.
The cycloalipatic diepoxides are preferred.
The amount of diepoxide charged to the re-
action can vary from about 0.2 mole per mole of ester
diol alkoxylate II initially charged to the reaction to
as high as one mole of diepoxide per mole of ester
diol alkoxylate II. Preferably i~ is from about 0.3
to 0.6 mole of diepoxide per mole of ester diol alk-
oxylate II initially charge Conventional epoxide
reaction catalysts are used.
Reaction of the ester diol alkoxylate II
with an epoxide is conducted at a temperature of from
about 100CC to 250C, preferably from about 140C to 160C
~,.' 1,
~ 7 11855-C-l
in the presence of the known c~nventi~nal cat~lysts.
m e tLme requ$red will vary depend~r.g upon the par-
eicular reactants charged, catalyst, temperature, and
batch size of the reaction mLxture, facts which are
well known to those skilled in the art. Generally,
lt has been f~und that a re~ction period of from 2 to
lQ hours from ~bout 140 to 200C, is adequate to pro-
duce the epoxide-modified product. This product can be
used per se or ie can be capped or modified with a
carboxylic ~cid anhydride by the reaction of this hy-
droxyl terminatet epoxide modified ester diol alkoxy-
late V with an intramolecular carboxylic acid anhydride
by the same procedures hereinbefore described for pro-
ducing the 2nhydride modified ester diol alkoxylates III.
In th~s i~stance the compounds produced can be repre-
~ented by the general ~chematic formula:
V A
COOH COOH
~COO~ O /~ OOC ~J
OH OH
which shows the product obtained by reaction of V with
phthalic anhytride when fully capped.
Fcrmulated ComPositions Usin~ PolYols
The dified ester diol alkoxylate derviatives
of the types represented by formulas III, IV, IV A, V
and V A can be formulated to produce coating and ink
14.
~ 7 11855-C-l
compositions by the addition thereto of crosslinkers,
polyols, pigments, fillers, ~nd other additives con-
ventionally used in the production of cDatings and
~nks.
In producing ehe formulated compositions
a crosslinker such as a ~ethylolated mel~ine can be
used in an amount from 25 to 200 weight percent, pre-
ferably from 25 to 100 weight percent, of the modified
ester diol alko~ylate charged. These compounts are
well known and m~ny are commercially available. Those
suitable for use can be represented by the general
formula:
1 2
J~ J~
v~rJ N ~"2
wherein X is hydrogen or -CH20CH3 and wherein ~t least
two of the X substituents ar,e -CH20CH3 groups. The
preferred melæmine derivaeives are the highly methyl-
2Q ola~ed melamines) with hex~methoxymethylmelamine mostpreferred. Other amino resins that can be used include
the urea znd benzoguanamine resins.
In addition one can have present a non-volatile
low lecular ~eight polyol containing from 2 to 6,
preferably 2 to 4 hydroxyl groups. m ese ncn-volatile
low lecular weight polyols can have a molecular ~eight
of from 62 to about 1000. They can be aliphati~ cyclo-
~liphatic or ~rom2tic in nature. Illustrative thereof
one ~an mention ethylene glycol, diethylene glycol, tri-
ethylene glycol, propylene gylcol, dipropylene glycol,
150
07
11855-C-l
neopentyl ~lycol, butyle~e glyc~l, 2,2-d'meehyl-3-
hydroxypropyl 2r2-d~mPthyl-3-hydroxypropiondte, 2,
3-dibromo-1,4-but-2-ene diol, bisphenol- A and the
ethylene o~ide ~nd/or propylene oxite adducts there-
of, 2,2-dihydroxy~ethylpropionic ac~d, trimethylol
ethane, trimethylol propane, pentaerythr$tol, di-
pentaerythritol, glycerine, sorbitol, hydrogena~ed
bisphenol-A; l,l-dihydroxy methane cyclohexane, 2,2'-
dihydroxymethylbicyclo [2.2.1~heptane, 1,5-pentane
diol, decane diol, and the like. Many other non-
volatile low molecular weight diols having a molecular
weight of fr~m 62 to about 1000 are known and can be
used; the above enumerati~n is illustrative ~nly.
Further, one can have present any of the
known polycaprolactone polyols that are co 2 ercially
a~ailable and ~hat are fully described, ~or eYample
ln U.S. 3,169,94~. As described in this patent the
polycaprolaceone polyols sre produced by the catalytic
polymerization of sn exces of a caprolactone and an
organic polyfunctional ~nitiatDr having at least two
reactive hydrogen atoms. The method for producing the
polyc~prolactone polyols i~ of no consequence and the
organic functional ini~iator~ can by any polyhydroxyl
- compound aR is ~hown in U.S. 3~169J94~. Illustr~tive
thereof ~re the diol~ Cuch as ethylene glycol, diethyiene
glycol, ~riethylene ~lycol, 1,2-propylene glycol,`dipro-
pylene glycol, 1,3-propylene glycol; polyethylene ~lycol,
polypropylene glycol, poly ~oxyethylene-oxypropylene)
glycols, and sim~lar polyalkylene glycols, either block-ed;
capped or heteric, containing up to about 40 or more
16.
~ 7 118jS-C-l
alkyleneoxy units in the molecule~ 3 methyl-1-5-pentane-
diol, cyrlohexanediol, 4,4'methylene-bis-cvclohexanol,
4,4'-isopropylidene bis-cyclohexa~ol, xylenediol, 2-(4-
hydroxymethylphenyl) ethanol, 1,4 butanediol, and the like;
triols such as glycerol, t~imethylolpropane, 1,2,6-hexane-
~ triol, triethanolamine, triisopropanola~'ne, dr.d the like;
tetrols such as erythritol, pentaerythritol,
~,N,N',N'-tetrakis (2-hydroxyethyl)ethylene diamine, and
the like.
lQ When the organic functional initiator is re-
acted with the caprolactone a reaction occurs that can
be represented in its s~mplest form by the equation:
O
R '(OH)X + 0~1 ~CHR' ~ R"( [OC(CR 2)4CHR ]mOH)X
O
In this equation the organic functional initiator is the
R"-(OH~ compound and the caprolactoné is the
O~C(CR'2)4CHR
~
compound; this c~n be caprol2ctone itself or a substituted
csprolactone wherein R' is an alkyl, alkoxy, aryl, cyclo-
alkyl, alkaryl or aralkyl group having up to twelve car-
bon atoms and wherein at least sLX of the R' groups are
hydrogen atoms, as shown in U.S. 3,169,945. The poly-
caproLactone polyols that are used are shown by the formu-
la on the right hand side of ~he equation; they can h ve
an svera~e molecular weight of from 290 to about 6~000.
11~55 ~-1
~he preferred p~lycapr~lsctone polyol compounds are those
having an avera~e molecular weight of from about 290 to
about 3,000, preferably fr3m sbout 300 to 1,000. The
m~st pref~rred ~re the polycaprolactDne diol compounds
having an sverage lecular weight of from 290 to about
500 and the polycaprolactone triol com~ounds having an
average molecular weight of from about 300 to about 1,000;
these are st preferred because of their low viscosity
properties. In the formula m is an integer representing
lD the average number of repeating units needed to produce
the compound havin~ said molecular weights. The hydroxyl
number of the polycaprolactone polyol can be from about
15 to 600, preferably from 200 to 500; and the polycapro-
lactone can have an average of from 2 to 6, preferably 2
to 4, hydroxyl groups.
Illustrative of useful polycaprolac~nes that
can be used in the formulated com~ositions oRe can men-
tion the reaction products of a polyhydro~yl compound
having an average from 2 to 6 hydro~yl groups with capro-
lactone. The manner in which these type polycaprolactonepolyols is produced is shown in U.S. 3,169,945 and many
~uch com~ositions ~re commercially available. In the
following table there are listed illu~trative polycapro-
lactone polyols. The first column lis~ ~he Gr~anic
funct~onal initiator that is reacted with the caprolac-
tone ~nd the average molecular weight of the polycapro-
lactone polyol is shown in the second column. Knowing
the molecular wei~hts of the initia~or and of-the poly-
~ 7 11~55 C-l
c~prolactone polyol one can readily determine the
average number of mDlecules of caprolactone (CPL Units)
that reacted to prDduce the polycaprolactone polyol;
this figure is shown in the third column.
IYPE A POLYCAPROLACTONE POLYOLS
Average Average No. -.
M~ ofof CPL units
Initiator ~olyolin m~lecules
1 Ethylene glycol 290 2
2 Ethylene glycol 803 6.5
3 Ethylene glycol 2,114 18
4 Propylene glycol 874 7
5 Octylene glycol 602 4
Decalene glycol 801 5.5
7 Diethylene glycol 527 3. 7
8 Diethylene glycol 847 6.5
9 Diethylene glycol 1,246 10
Diethylene glycol 1,998 16.6
11 Diethylene glycol 3, 526 -30
12 Triethylene glycol 754 5. 3
13 Polyethylene glycol (MW 200~* 713 4.5
14 Polyethylene glycol (M~ 600)* 1,398 7
Polyethylene glycol (MW 1~00)* 2,868 12
16 1,2-Propylene glycol 646 5
17 1,3^Propylene glycol 988 8
18 Dipropylene glycol 476 3
19 Polypropylene glycol (MW 425~* 835 3.6
Polypropyle~e glycol (~W 1000)*1,684 6
21 Polypropylene glycol (~ 2000)* 2,456 4
22 Hexylene glycol 916 7
23 2-Ethyl-1,3-hexanediol 602 4
24 1,5-Pentanediol 446 3
1,4-Cyclohexanediol 629 4.5
26 1,3-Bis(hydroxyethyl)-benzene736 5
27 Glycerol 548 4.
2~ 1,2 ,6-Hexanetriol 476 3
29 Trimethylolpr~pane 590 4
30 Trimethylolpropane 750 5.4
31 Trimethylolpropane 1,L03 8.5
32 Triethanolami~e 890 6.5
33 Erythritol 920 7
34 Pentaery~hritol 1,219 9.5
* - Average lecular weight of glycol.
The stru~tures of the compounds in ~he above tabu-
lation are obvious to one skilled in the art b~sed on
lg.
11855 -C-1
the information given. The structure of compound No.
7 is:
O
~ 10[(C~12)5co]rc~2cH2ocH2cH2[o~cH2)5~roH
wherein the variable r is sn integer the 8um of r + r
has sn average value of 3.7 and the ~verage lecular
weight is 527. The structure ~f compound No. 20 is:
~O~(CH )5~0~ (c3H6o)~ ~3H6[0~(CH2)5]r
1~ wherein the sum of r ~ r has an average value of 6
and the average lecular weight is 1,684. This ex-
planation m~kes explicit ~he structural formulas of
com~ounds 1 to 34 set forth above.
The concentration of the modified ester diol
alkoxylate derivatives of the types represented by for-
~ulæ I~I, IV, IV A, V and V A in the formulated com~o-
s~tions can be from 20 to 80 weight percent, preferably
from 25 to 50 weight percen~.
The coating compositions can also contain an organic
~olvent and a catalyst as optional components. Any of
the conventional solvents used in the coatings industry
can be used at a concentration preferably below 30 weight-
percent of the total weight of the coating composition.
While larger ~mounts could conceivably be used, the use of
larger amounts would destroy the hi~h solids na~ure ~f the
coat~ng, ~olve~t.s are generally added in the small a unts
20.
~ 7 11855-C-l
indicated to improve flowability during application
of the coating com~osition to the substrate.
In some instance an acid catalyst might be desire~
to improve the efficiency of the melamine crosslinking
reaction during curing. The concentration of the cat-
alyst can vary from zero eo about 10 we,ght percent
based on the total ~eight of the coating composition.
The particular catalyst used ~nd its concentration are
dep~ndent to a degree upon its catalytic activity and the
~ specific components present in the coatings composition.
Ihese catalysts are known to those skilled in the
art and include hydrochloric acid, sulfuric acid, p-tolLene
sulfonic acid, dodecylbenzene sulfonic acid, phosphosic
acid and its alkyl derivatives, m2leic acid, trimel-
litic acid, phthalic acid, succinic acid, and the like.
The coatin~s compositions can also contain pigments,
fillers and other additives conventionally present in
coatings compositio~s in their conventional quantities.
The particular ones selec~ed are of no consequence to ~he
basic invention. In preparing the coatings compositions,
the ingredients are mixed by the conventional procedures
uset in the production of paints, inks or coatings compo-
sitlons. These procedures are so well known to those
skilled in the art that they do not require further dis-
cus~ion here.
The coatings compositions are applied to a surface
21.
~ 07 11855-C-l
or substrate by conve~tional means and then thermally
cured by heating at a temperature ~f about 125 to 250C,
preferably from 150 to 200C, for a period of time suf-
ficient to obtain a d~ film. Generally, this time will
ran~e from about one tc 30 minutes, preferably from 10 to
20 minutes. The components present in a particula- hig~
solids coating c~mposition will determine the temperature
and time that will be required to obtain an adequate cure
and 2 good film coating.
The coatings compositions of this inventio~ are high
solids coatings compositions and they can contain as much
as 90 weight percent or more solids therein. Generally
the total solids content of the coatings compositions of
this invention range from about 70 to 90 weight percent
of the total ~eight of the coating composition.
Modified Latex C~mpositions
It has also been found that the mDdified ester
diol alkoxylate derivatives of the types represented by
formulas III, IV, IV A, V and V A can be added to lat~x
compositions to ~mprove the properties of the latexes;
in particular ~crylic latexes.
m e latexes that can be used are known to those
skilled in the srt and include acrylic acid and meth-
acrylic acid derived latexes 8S well as those latexes
derived from their esters. m ese latexes are commerci~llv
available and are known to be copolymers of two or m~re
22.
l~Z~)7 11855-C-l
monomers such ~s methyl methacrylate, styrene, methyl
acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl
acrylate, butyl methacrylate, methacrylic acid, acrylic
acid, 2-hydroxyethyl acrylate, ~inyl chlorite, vinyl
acetate, acrylamide, 2-hydroxypropyl acrylate, iso-
butoxymethyl acrylamide, maleic acid, glycidyl acrylate,
vinylidene chloride, vinyl ethyl ether, butadiene,
acrylonitrile, diethyl maleate, vinyi ethyl ketone, and
t~e like. Illustrative of copolymer latexes are vinyl
chloride/vinylacetate/methacrylic acid, stryene/ethyl
acrylate/methacrylic acid, methyl acrylate/styrene/
vinyl acetate/methacrylic acid, and any other known
latex.
The a unt of said modified ester diol alkoxylate
deriva~ive that can be added to the latex can vary from
about 5 to about 50 weight percent, based on th~ total
solids content of the latex, preferably from 10 to 20
weight percent. It is added to the latex and stirred
in by conventional means to obtain uniform distribution
therein. The latex formulation can also contain other
components generally present in latex coating compositions
such a~, surfactants, antifoams, bactericides, mildewicides,
other coalescing acids, freeze-thaw additives, light
stabilizers, and the like. These are well known to
those skilled in the art, as are ~he amounts thereof
required in l~tex coatings, and do not need extensive
description or discussion herei~ _o enable one skilled
~ 7 11855-C-l
in the art t3 understand their use.
The latex c~atin~ compositions are applied to a
substrate by the known conventional methods. They are
cured by heating at a temperatu-e of a~out 125~ to 250C,
preferably from 150 to 200~C. for a period of time
sufficient to obtain a dry fi~m. Generally, this time
will range from about one to 30 minutes, preferably from
10 to 20 minutes. The components present in a particular
iatex coatin~ composition used will determine the tempera-
~ure and time that will be required to obtain an ade-
quate cure and a good film coating.
In the following exa~ples the products were evalu-
~ted according to the following procedures.
Crosshatch adhes _n refers to a test using 10 paral-
lel, single-edge, razor blades to scribe test fiims with
sets of perpendicular lines in a crosshatch pattern.
Ratings are based on the amount of film removed after
applying and subsequently pulling a contact adhesive
tape (Scotch Brand 606) away from the surface of a scribed
20 coating at a 90 degree angle in a fast, rapid movement.
It is Lmportant to carefully apply and press the tape to
the scribed co~ting to eliminate sir bubbles and provide
a good bond because adhesion is repor~ed as the percent
~f film remaining on the substrate with a 100 percent rat-
ing indicating complete adhesion of the film in the sub-
~trate.
_ol~ent resistance is a measure of ~he resis~ance of
24.
11855 -C-l
the cured fil~ to attack bv solvents, usually acetone
or ~ethvl ethvl ~etone, and is reported in the nu~be-
of double rubs or cvcles of sol~ent soaked cheese clo.~.
required to remove one-half of a fil~ from che test area.
The test is perfor~ed bv strokin~ the film with an
acetone ssturated cheese cloth until that amount of f il~
coating is re~oved. The nu~ber of cycles required to
remove this amount of coating is a neasure of the coa~-
ing solvent resistance. Values ~reater than 100 are
reported as 100 which ~eans less ~han one-half the fil~
was removed after 10~ double rubs.
Reverse impact resistance ~easures the ability of
a given fil~ to resist rupture from a falling weight.
A ~,ardner Im~act Tester usin~ an eig~-pound dart is
used to test the films cast and cured on the steel panel.
The dart is raised ~o a given height in inches and drop-
ped onto the re~erse side of a coated ~etal panel. The
inches ti~es pounds, desi~nated inch-pounds, absorbed bY
the fil~ without rupturing is recordet as the reverse im-
pact resistance of the film.
In this application, the following definitions define
certain co~pounds that are used in the exanples:
Silicone Sur actant I is
r ~H3- -CH3
(CH3)3SiO r SiO- _ -SiO L Si(CH3)3
L CH3_ 13 ~3H6(0C2~I4)70H
Epoxide A is 3,4-epoxycyclohexvlmethyl-3,4-epoxycyclohexane
car~oxylate~
25.
11855 -C-l
The f~llo-iing experiments show the production
of ester di~l ~lkoxylates II.
Preparation Of Ester Diol Alkoxvlates II
- Experiment A
-
A reactor ~as charged with 408 grams of freshly
stripped solid 2,2-dimethyl-3~hydroxypropyl 2,2-dim- -
ethyl-3-hydroxypropionate ~nd 1.39 grams of potassium
metal as cat~lyst and heatet to liquify the solid. The
reactor was purged with nitr~gen and then over ~ lO hours
addition period 528 grams of ethylene oxide were added
while maintaining a temperature of from 106 to 114C.
After all of ~he ethylene oxide had been added, the re-
action was continued at 114C. for 30 minutes 'co com-
pletion. The reaction produc~ was neutralized with 1.69
grEms of acetic ~cid and vacuum stripped at 60C. and
1 mm of Hg pressure. The liquid ester diol ethoxylat~
secovered weighed 922 grams as the residue product con-
taining a mi~or amount of by-products.
The ester diol alkoxylate produced had an average
of about 3ix (~ + y of Formula II) ethyleneoxy units in
the m~lecule. m e average molecular wei~.t was 480, the
Brookfield viscosity W2S 194 CpS. at 26C. ~No. 3 spindle,
100 rpm.)~ the specific gravity was 1.079 g/cc and the
Gardner color was less ~han 2. Ihe water dilutability
was 250. Water dilulability defines the gram~ of water
that c~n be ~dded to lO0 gra~ of the ester diol ~lkoxylate
to achieve a haze point.
~ 6.
11855-C-l
llfl~ {)7
Exper~ent B
Following the proredure similar to that described in
E~periment A, 792 grams of ethylene oxide and 612 grams
of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hytroxy-
~ propionate were reacted using 2.1 grams of potassium
catalyst. The ethylene oxide feed time was about 11
hours.
The liquid ester diol ethoxylate residue productproduced wPighed 1,391 grams; it had an aver~ge of
a~out six ethyleneoxy units in the molecule. The average
molecular weight was 477, the Brookfield viscosity was
200 cps. at 24.5C (No. 3 spindle, 100 rpm), the specific
gravity was 1.08 g/cc and the Pt/Co color was 60 Water
dilutability was 296.
Ex~eriment C
Following the procedure similar to that described
in Experiment A,528 grams of ethylene oxide and 612 grams
of 2,2-dimethyl-3-hydrsxypropyl 2,2-dLmethyl-3-hydroxy-
propi~nate were reacted using 1 gram of potassium as
cat~lyst. The ethylene oxide feed time was about 9 hours.
The liquid esterdiol ethoxylate residue produc~ pro-
duced weighed 1,128 grams; it has an average of about
four ethyleneoxy unies in the molecule. The average
molecular weight was 392, the Brookfield ViscGsity was
168 cps. at 27C ~o. 3 spindle, 100 rpm), the specific
27.
ll~Z~7 11855 -C-l
gr~vity ~as 1.07 g/cc and the Pt/Co col~r was 40. Water
dilutability was 200.
Experiment D
Foliowing the procedure similar to that described
~n Experiment A 220 grams of ethylene oxide ~nd 510 gr~ms
of 2,2-dimethyl-3-hydroxypropyl 2,2-dimRthyl-3-hydroxypro-
pionate were reacted using 1.1 grams of potassium ~s cat-
alyst. me ethylene oxide feed time was a~out S hours.
The liquid ester diol ethoxylate residue product
produced weighed 730 grams; it had an average of about two
ethyleneoxvunits in the molecule. The average mDlecular
weight was 2g5, the Brookfield viscosity was 285 cps at
25C. (No. 3 spindle, 100 rpm) and the Pt/Co color was
75. Water dilutability was 86.
~=~
A stainless steel autoclave was charged with 3,011
grams of solid 2,2-dimethyl-3-hydroxypropyl Z,2-dimethyl-3-
hydroxypropionate ~nd 18 grams of boron trifluoride etherate
and the contents were heated to 60C. Then the autoclave
was pressured to 10 psi with nitrogen and the ethylene oxide
feed was searted. A total of 2,604 grams of ethylene oxide
was added over a period of about six hours while maintaining
the reactor ~emperature of 65 to 68C. and the pressure between
1~ and 30 psi. After all the ethylene o~ide had been ~dded
the temperature was maintained at 65UC. until no ethylene oxide
pressure remained in the reactor. The product was cooled to
40C; 2 weight percent of magnesium sili~ate neutralizing agent was
28.
11855 ~-1
~ 0 7
added and the mixture was stirred at 40C. for one
hour. The temperature was raised to 90C. and held
while a vacuum was applied to remove vol~tile products.
This vacuum was continued until the pressure in the
reactor reached 5 mm. of mercury. The clear/colorless
product was pressure filtered to rem~ve insolubles.
m ere was recovered 5,494 grams of the li~uid ester diol
ethoxylate residue product having an average of about
four ethyleneoxy units in the molecule. Ihe average mole-
cular weight was 382, the Cannon Fenske viscosity was
90 cks at 100F. ~nd the Pt/Co color was 30; it had anacid value of 0.06 percent as acetic acid. Gas chro~Ato-
graphic analysis indicated that the product was free of
neopentyl glycol ~nd its ~dducts.
In a similar manner the mixed ester diol ethoxylate/
propo~ylate is produced using a mixture of ethylene oxide
and propylene ~ide as the feed ~tPrial. Likewise, the
ethoxylatelstyroxylate is produced.
Experiment F
~ Following a procedure similar to that described in
Experiment A, 204 grams of 2,2 dimethyl-3-hydroxypropyl
2,2^dimethyl-3-hydroxypropionate and 440 Rrams of e~hylene
oxide were reacted at 99~ to 115C. using 1.5 grams of
bor~n trifluoride etherate ~s the catalyst. The ethylene
oxide feed time w~s about 4.5 hours and the mixture was
29.
11855~-1
heated an ~dditi~nal 0.75 hours after co~pletion of the
addition. Then 13 grams of magnesium silicate were added
and the mixture was stirred overnight At 50 to 65C. It
was filtered, then stripped at 100C. for one hour to a
pressure of 5mm. Hg.
The liquid ester diol ethoxylate residue product
produced weighed 602.4 ~rams; it had an average o~ nbout
10 eehyleneoxy units in the molecule. The Brookfield
viscosity was 193 cps at 30C. (No. 3 spindle, 100 rpn)
the specific gravity was i.046 g/ec and the Gardner
color was 1.5. Water dilu~ability was 15.6
ExPeriment G
Following the procedure described in Experiment
F, 204 grams of 2,2-dimethyl-3-hydroxypropyl 2,2-dim-
ethyl-3-hydroxypropionate was reacted with 440 grams of
ethylene oxide using 1.5 ~rams of boron trifluo~ide ether-
ate as the catalyst. The ethylene oxide addition time was
about 7.5 hours.
The liquid ester diol etho~ylate residue product
2~ produced weighed about 629 grams after filtering and
stripping. It had an average of about 10 ethyleneoxy
units in the molecule. The Cannon FenSke viscosity at
100F was 103.4 cks., the specific viscosity was 1.046
g/cc and the Gardner color was 1. Water dilutability
~as 15.4
Experiment P.
Following the procedure described in Expesimen~ F,
30.
il'~Z~)7
11855 -C-l
125 ~r~s of 2,2-dimethyl 3-hydroxypr~pyl 2-2dimethyl-3-
hydroxypropionate was reacted at 48 to 132C with a
total ~f 502 ~rams of ethylene oxide using a total of
1.3 grams of potassium as the catalyst. The ethylene
oxide feed time was about 9.5 hours. At the completion
of the feed 11.9 grams of ma~nesium silicate were added
and the mixture was stirred for one hour and then cooled.
Ihe ester diol ethoxylste was filtered hot and stripped
under vacuum.
The stripped ester diol ethoxylate residue product
recovered weighed about 585.3 grams. It had an average
of ~bout 19 ethyleneoxy units in the molecule. The Cannon
Fenske viscosity was 115.5 cks at 100F. On standing
it solidified at 25C. and melted at about 27C.
ExPeriment I
In a manner similar to that described in Experiment
A, 805 grams of 2,2-dimethyl-3-hydroxypropyl 2,2~dimethyl-
3-hydro~ypropionate and 8 grams of boron trifluoride
etherate were melted at 60C in a reaction flask. Over
a period of about 1.75 hours a total 811 grams of pro-
pylene oxide were added at a temperature of 57 to 60C.
The reaction mixture was stirred about another 2 hours;
32.3 grams of magnesium silicate were added and stirred
at about 70C for about 1.5 hours. It was then stripped
at 70~C for 0.5 hours at 4-5 mm. of mercury and filtered.
The liquid ester diol propoxylate residue product was
31.-
~ 7 11~55 -C-l
clear ~nd c41Orless and w~ighed 1,50~ grams. It had
an average of qbout 4 propyl~eo~ units in the m~lecule.
Ihe following examples serve to further define this
invention; psrts are by weight unless otherwise indicated.
Pre~aration Df Anhydride Modified Ester Diol
Alkoxvlates III And Formulations Thereof
ExamPle_ 1
Part A - A glass-lined autoclave was charged with
429.47 par~s of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl
-3-hydroxypropionate ~nd 2.4 parts of boron trifluoride
etherate. The mixture was heated to 55C and 370.5 parts
of ethylene oxide were added over a period of about 13
hours. This mixture was then held at this temperature
for four more hours. Then, 2 percent by weight of mag-
nesium silicate was added and the contents were heated to
90C and stirred for 4 hours. Thereafter the pressure was
reduced to 20 mm Hg and the,product was stripped for four
hours to re ve volatiles. AtmDspheric pressure was re-
stored with nitrogen, the contents were cooled to 50C,
and transferred to a storage autoclave. Five parts of filter~id were added, ~he contents were m~xed for 30 minutes,
and then filtered and stored. A second batch was made
in the sæme manner and both batches were bl~nded by plac-
ing the materials in a large autoclave, heating the con-
tents to 90C, and stripping the pr~duct 4 hours at 5 mm
Hg. There ~as obtained a large quantity of the liquid
ester diol ethoxylate havillg an average of about 4 ethylene-
oxy units ~n the lecule.
32 .
1185~ C-l
Part B - A 236.7 ~rams p~rtion of the above liquid
ester diol eth~xylate (Part A) was charged to a re-
~ctor together with 163.3 gr~s ~f phthalic anhydride
and 96 grams of 2-ethoxyethyl acetate as the solvent.
The ~i2ture was stirred and heated at 140C for 30
minutes. The anhydride modified ester diol ethoxylate
III had the following average structural formule:
COOH COOH
~CO(O C2H4~xCH2C CH200C C Q20(C2H40)yOc~
~n whieh the sun ~f x and v have an average ~alue of about 4.
The mixture ~lso contained unreacted ester diol ethoxvlate
It had a Brookfield viscosity of 386 cps at 25C and
an ~cid number of 124 mgm. KOH/gm.
?art C ~ A coatiLng ~om~osition was prepared by mixing
10 grams of the above anhydride modified ester diol
etho~ylate (Part B), 10 grams of hexamethoxymethylmela-
mine, 0.5 gram of N,N-dimethylethanolamine, 3 grams of
distilled water, and 0.05 gram of Silicone Surfactant I.
Films were prep~red by casting the above composition on
steel pannels wi~h a No. 40 w~re-wound rod and thermally
curing in a circulating 2ir oven. Curing for 20 minutes
at 220F afforded no cure. Curing for 20 minutes at 250F
produced films with a 4B pencil hardness, 43 acetone rubs,
6nd greater than 320 inch-pounds reserve im~act resistance.
In this compo~ition, cure was achieved even in the ab-
sence of catalyst.
ll;~Z~07
11855-C-l
E~am~le 2 - A coating com~osltion was prepared by mixing
10 grams of the ~nhydride mDdified ester diol alko~y~ate
(Psrt B) of ~xample 1, 10 grams of hexamethoxymethylme-
lsmine ~s crosslinker, 0.5 gram of N,N-dimethylethanola-
- mine, 3 grams of distilled w ter, Q.05 gram of Silicone
Surf~ctant I, ~nt 0.2 gram of a 40 percent solution of
p-toluenesulfonic acid dissolved in ~n organic solvent
as the catalyst. Cured fi~ms were prepared as described
~n Example 1, Part C. ~uring for 20 minutes at 220F
afforded fiLms with 100 acetone ru~s, F pencil hardness,
and hi~h reverse i~act resistance. A film cured at
250F for 20 minutes achieved a 2H pencil hardness, 100
acetone rubs, and high reverse lmpact resistance. The
im~roved properties obtained by the use of a cure cat-
alyst are clearly evident.
E~ample 3 - A s~eries of high solids ~oating compositions
was produced by mixing 10 g~ams of the anhydride modifi-
ed ester diol ethoxylate ~Part B) of Exam~le 1, Ep~xide A,
stannous octoAte catalyst, 0.1 gram of Silicone Surfact~nt
I, and 1 gram of xylene. Film3 were prepared from the
8S weight percent solids solution as described in Example
1 Part C. Curing at 200F for 20 minutes produce~ clear
dry films. m e quantities o~ reactants used and proper-
ties of the cured films are tabulated below; all ~he films
were sm~othwith high gloss.
34.
11855-C-l
Experime~ts
Formulation A B C D
Example 1, Part B 10.0 10.010.0 10.0
Product, g
- Epoxide A, g 15.0 10.0 7.5 6.0
Stannous Octoate, g O.23 0.180.15 0.14
CoatinR Properties
Reverse Impact 5 250 ~ 320 300
~n-l~s.
Acetone Ru~s 100 100 92 68
Pencil Hardness H 2H 2H . 2H
______ _____________
For~ulat~nB represents the optimum therEDset characteris-
tics. The C and D formulation5describe the decrease in
thermoset characteristic~ that occur when the amount of
epoxide is decreased and the re~ultant high impact snd
hardness that ~ achieved at the cure conditions used.
FormulationA is a hard coating with e~cellent ~hermoset
2~ characteristics-
E~amPle 4 - A pigmented high ~olids coating composition
was produced by blending 100 græms of the anhytride modi-
fied ester diol ethoxylate of E~ample 1, 180 grams of
titanium dio~ide pigm~nt, 3 grams of stannous octoate cat-
slyst, 1 gram of Silicon~ Surf~c~ant I, ~nd 40 grgms of
xyl~ne In 8 ball m~ vernight. Subsequently, 61.73 grams
of Epoxide A ~nd 30 græms of xylene was mixed with 200 grams
of the above mixture to afford a 77 ~ight percent solids
co~ti~g compositlon with ~ Br30kfield viscosity of 180
35.
~ 11855-C-l
centipoises at 25C. FiL~s pre?ared according to the
procedure descr~bed in Example 1 were c~red at 220F
for 20 minutes. The fiLm produced passed 100 acetone
rubs, had high gloss, had excellent adhesion an~ achie-
ved a pencil h~rdness of 2H.
~ ExamPle 5
Part A - A 360 grams portion of ~he liquid ester diol
ethoxylate of Part A of Example 1 was reacted with 40
grsmc of phthalic anhydride for 30 minutes at 140C
1~ ~O produce ~ phthalic modified ester diol eehoxylate
having a Brookfield viscosity of 500 cps and an acid
~u~er of 40 mgm. KOH/gm.
In ~ similar manner succinic anhydride can replace
phthalic anhydride.
Part B - A coating com~osition was produced by ~ xing
100 grams of the above product of Part A with 100 grams
of hexamethoxymethylmelam~ne, 140 grEms of titanium di-
o~ite, and 25 gr~m~ of 2-ethoxyethyl acetate. The mix-
ture was mixed overnight in a ball mill. Then a 158.5-
gram portion was separated and mixed with 1 gram of phos-
phoric acid catalyst and 25 fldditionsl grams of 2-ethoxy-
ethyl acet~te. Films prepared by the procedure described
in Example 1 were cured for 20 minutes at 300F. The
film had good solvent resista~ce (m~re than 100 acetone
rubs), good adhesi3n, ~nd 75 inch-pounds reverse impact
resistance.
36.
7 11855-C-l
l e 6
Part A - A 320 ~rams portion of the liquid ester diol
eth~xylate of Par~ A of Ex~aple 1 was reacted wlth 80
grams of phthalic anhydride for 30 minutes at 140C
to produce 8 phthalic modified ester diol ethoxyLate
~ having ~ Brookfield viscosity of 1,690 cps and an acid
num~er of 77 m~m. ROH/gm.
Part B - A co~ting composit~ was produced by charging
100 grams of the product ~f Part A, 100 grams of hexa-
methoxymethylmelamine, 140 grams of titanium dioxideS
and 30 grams of 2-ethoxythyl acetate to a ball ~ill and
rolling it overnight. Then a 163.5-~ram po-tion of the
mixture was blented with 1.5 grams of phosphoric acid,
0.42 gram of Tinuvin 770 ~ (a W stabilizer marketed
~y Ciba-Geigy), 0.11 gram of Irganox 1010 ~ (a branched
phenol antioxidant marketed by Ciba-Geigy), 50 grams of
2-e~hoxyethyl 2cetate, and 4.55 grams of a polycapro-
lactone triol having an average molecular weight of 300
and sn average hydroxyl number of 56~. Films were pre-
pared accor~ing to the procedure described in Example 1
and cured for 20 minutes at 250F. The film produced was
solvent re.qist~nt (more than 100 ace~one rubs~, had a
pencil hardness of 2B, and passed 50 inch-pounds reverse
im~act resistance.
Exam~le 7
Part A - A 280 gr~ms portion of the liquid ester diol
ethoxylat? of Part A of Example 1 was reacted wi~h 120
~ 07 1185~
~rams of phthalic anhydride for 30 minutes at 140C.
to produce a phehalic ~Ddified ester diol echoxylate
having a Br~okfield viscosity of 18,280 cps and an
ac~d number of 115 m2m. KOH/gm.
Part B - A costing composition w~s produced by charg-
~ ing 1~0 grams o~ the product of Part A, 100 grams of
hexamethoxymethylmelamine, 140 grams of titanium di-
oxide, and 40 grams of 2-ethoxyethyl acetate to a ball
mill and roll~ng the mixture overnight. Then a 173 gram
portion of the mixture was blended with 1.5 grams of
phosphoric ~cid, 40 grams of 2-ethoxyethyl acetate,
~nd 4.5 grams of the polycaprolactone triol used in
Exam~le 6, Part B. A film was prepared according to
theprocedure described in Exam~le 1 and cured ~or 20
minutes at 259F. ~he film produced was solvent re-
~istant ~ore than 100 acetone rubs) and h~d a re-
verse impzct resistance of 200 inch-pounds.
Pre~aration Of IsocYanate M~dified Ester Diol
Alkox~lates IV And IV A And Formulations Thereof
ExamPle 8
Part A - A series of iso~y~nate m~dified ester diol
e~hoxylates was psepared by reacting the ester diol
ethoxylate of Part A of Example 1 with 3-isocyanato-
methyl-3,5,5-tr~methylcyclohe~ylisocyanate (IPDI) 8~
45C for about ~ hours. The resulting pro~uc~s con-
tained unreacted ester diol etho~ylate and i~s hydro~yl
~z~07 11855 -C-l
terminated diureth~ne dervative. The quantities re-
acted and properties of the product mixtures produced
are ta~ulated below:
Run (1) (2~ (3) (4)
Exam~le 1, Part A, g! 95 90 80 85
IPDI, g 5 10 20 15
Stannous octoate, g 0.1 0.1 0.1 . O.1
Product ProPerties
Brookfield viscosity, 512 1,588 33,000 6,000
cps at 25C
Water dilutability, gms.
water/100 ~ms. prDduct
to h~ze point. 1~6 78 21
Part B - Aqueous co~ting compostions were formulated and
cur d following the procedures described in Exam~le 1,
Part C. The data are summ~rized in the following table:
39 .
11;~26{)7
11~55~
~ ~' g _ o ~
_ _ ~ ~ _
-- O r~ o -- O , U2
_ _ _ C
~ ~ 8 s ~ _ .
_ ~ o
._ L
l O ~ o ~ g g ,Q ~ O
~1 ~ ~ o ~ ~ -- ~
_ O ".~ - 3
~ ~ o 1~
. ~ . , ~ ~ ~ 8~ g Y o , ~ `.
, , ~ o
_ C)
o~ ", o = "~, C
~ ~ ~ F
O o -- O o O ~ ~1
~ , o ~ o ~
, ~n 0, ~ ~
o , ~ o O O ~ 0 ~ g 2: 0 ' E
~ ~ -- ~ o ~,
_ ,,' _
8 ~
~., .,. _ o ~ .,
o o o ~ 8 2 g C
F,
~ ' U:
~ ~ ~ .
a ,~ e
c ~ b
o ~ ~ 0 ~ o e ~ ~ c _ , u
C _ - - ~ 3 6 ~ 1~ ~ t I~
Ei El ~; ~ o ~ ~
O b " ~ X '~ O ~ CJ
1~. ~ ce ~ 3 ~ *
40.
Z~7
11855 {~-1
_ o '^ 0
o o _ c ~ o
~ ~ C ~ U,
_ . c
_ ~
~ , , o o . -- 8 r~ 2 - ~ C
_ ~ ~ C ~ ~
~'
_ a
o ~ o = 3
~ ~
o o ~ o ~ o
_ a~ C ~ o ~
c
_ ~q
UO~V~ oO
, o I o ~ o 8 g -- ol
o~ , , ~ , _ ~ ~ o
O ~ o r,
~ o o s
o o ~ o ~ o
0 ~ 2 ~ 5 c = E
_ , i_
u~ u. O = o c
. ~
, , ~ , o o. ~ ~ ~ o ~ ' u
,~ .o ~ ~ o ~ ~ _ w _ .
_ _ CJ
-
o:
. '
E o
~ ~ C
, ~ ~ ~ _ 8 ' ~ c ., ~ , ,
I ~ ~
~ C ,, ~ .,
1~ t~ " C ~ _~
~ O a ~ u
_~ ~ ~ Q O O L Q. 1~. ~ 90 -- c
o I V ~ ~ C IU t c ~ C
O _ .~C) ^
E E E ~ ~ o ~ U ~ ' ~,~
O. 3 tl~ ~ V ~ `3
41.
11;ZA; ~37 118S5-C-1
E~c a~F 1 e
Part A - A 160 gr~q portion of the ester diol ethoxylate
of Part A of Example 1 was reacted with 40 grams of IPDI
for 2 hour~ at about 50C in contact with 0.2 gram of
stannous octoate as catalyst to produce a mi~ture con-
tai3 ~ g ~re2cted ester dlol eeho~cylate asld its hydro~yl
_ terminated diurethane derivative.
~art B - To the above reaction mi~ture there were added
35.3 grams of phthslic anhydride ~nd 58.8 grams of 2-ethoxy-
0 eth~l acetate. The ~ture w~S heated for 30 minu~es140C. to pr~duce ehe phthalic anhydride partially
capped reacti~n product mi Yture.
Part C - A seri~s of CoAt~ng com~ositlons was prepared and
cured by the procedures described in E~ample 1. Coatings
1 to 4 were cured for 20 minutes at 350~F; coat~ng 5 was
cured at 250F. TSe com~osition ~nd properties are tab-
ulated below:
I:oatin~ 1 2 3 4 5
Fo~aulation. Pllrts
2~ Exam~le 9, Part B 8 10 12 10 10
~e~amethoxy~ethyl- 12 10 8 ld 10
meLamiD.e
Sil~co~e Surfaetant I 0.1 0.1 0.1 0.1 0.1
p-Tolue~esulfo~ic acid 0 0 0 1.25 1.25
Ethoxyethyl Acetate 2.0 2.0 2.0 2.0 2.0
Coatin~ ProPertie~
Reverse Im~act, in-lbs. 300 300 300 5 15
Acetane R~bs 14 lO0 100 100 100
Pencil Hartne3~ 4B H~3 HB 5H 3H
3D Adhesion, Z 100 100 100 100 lOU
42.
11855~-1
Preparati~n of Epo~ide M~d~fied Ester Diol
0
Part A - A 348 grams portion of the liquid e~er diol
etho~olate of Part A of E~ample 1, 52 gram~ of Epo~ide A
and 1.2 gra~ of stannous octoate (added in two portio~s)
were reacted at 150C for 10 hours. The epoxide dified
ester diol etho~olate produced e~ntained 0.~8 weight per-
cent unreacted Epo~ide A in the mixture.
P~rt ~ - A serie~ of aqueous coating eampostion was pro-
duced 3nd cured following the procedures described in Ex-
nmple 1. m e tata are summarized in the following table:
Coatin~ 1 2 3 4
Formulation~ ~arts
E~ample 10 Part A 8.0 10.0 12.0 14.0
Hexamethoxymethylmel ~mi ne 12.O 10.0 8.0 6.0
p-Tolu~ne~ulfonic acid 1.0 1.0- 1.0 1.O
Dlst~lled Water 2.0' 2.0 2.0 2.0
Silicone Surfactant I 0.1 0.1 0.1 0.1
ture Tamp... ~F 20 250 20 250 20 250 200 250
Coatin~ ProPerties
Reverse Impact~ in-lbs. 5 ~5 ~ 5 5 25 ~5 50 25
Acet~ne Rubs 10 100 10 100 10 100 100 100
Pencll Hardness 5~ 5~ 4H 5H ZH 5H F H
The results ~ndicate that hard, thermoset coatings were
prepared.
ExamPle 11
Part A - A mi~ture of 300 grams of the epoxide mDdified
ester diol ethoxal~te of Part A of Example 10, 75 grams
43.
Z~7
11855 {:- 1
of phthalic anhydride nnd 94 grams of 2-ethoxyethyl ~cetate
w~s hested and reRcted for 30 minutes st 140 C. to produce
the phthalic anhydride capped der~vative of the epoxide
dified ester diol ethoxylate h~ving a Brookfield vis-
- cosity of 500 cps Bt 25 C.
Part B - A coaeing composition was produced by blending
12.5 grams of the capped product of Part A ~bove, 10 grams
of hexamethoxymethylmelamine, 0.1 gram of Silicone Surfact-
cnt I, and 2 gra of 2-ethoxyethyl acetate. Fi~ms prepared
according to the procedure described in ExamPle 1 were
cured for 20 minutes Rt 350F. The cured fi~ms obtaine~
~chieved a B pencil hardness, iO0 acetone rubs, and 320
inch-pounds of reverse impact resistance.
PreParation of Miscellaneous Fromu~tions Usine
Polyol And Latexes
ExamPle 12
A eries of C08ting compositions was protuced
using various anhydride modified ester diol ethoxyla~es
produced supra in coniunction with 8 low molecular weight
polyol. The formulations and their coating properties
are tabulated below; all coatings were cured for 20 min-
utes ~t 25D~F.
4~.
~ ~ 11855-C-l
Coati.n~ 1 2 3 4 5 6
Formulation, parts
. _
E~ample 5, Part A Adduct 8.5 7.0 0 0 0 0
Example 6, Part A Adduct 0 0 8.5 7.0 0 0 _
Exam~le 7, Yart A Adduct 0 0 0 0 8.5 7.0
Trimethylolpropane (~) 1.5 3.0 1.5 3.0 1.5 3.0
~exametho~ymethylmelamine lO lO lO lO 10 lO
Phosphoric Ac~d 0.2 0.2 0.2 0.2 0.2 0.2
Sili~one Surfactant 1 0.1 0.1 0.1 0.1 0.~ 0.1
Etho~yethyl Acetate 2.0 2.0 2.0 2.0 3.0 3.0
Coating Properties
Reverse Impact, ~n-lbs. 100 ~5 25 ~5 75 C5
Acetone Rubs lQ0 lO0 100 100 lO0 100
Pencil Hardness 3H SH 3H ~H 3H 6H
A & esion, % lO0 100 100 100 100 100
All fi~s were clear,smDoth, glossy9 and therm~set in charac-
ter. A & esion ~as e~cellent. The formul~tions containing
the large amount of TMP were ver~ hard and as a result had
~inimal ~mpact resistance.
E~am~le 13
C02ting com~os~tions were produced si~ilar to
those described in Example 12 ~ut containing higher con-
centrat~ons of the Adducts s~d decreased trimethylolpropane
concentr~tions. The coatings ~ere cured at 250~F for 20
mi~utes. The results are tabulated belo~.
45.
Zti~)7
11855~-1
Coatin~ 1 2 3 4 5 6 7 8
Formul~tion. Parts
Example 5, Part A Adduct 9,0 9.5 0 0 O 0 0 O
Ex2m~1e 6~ Part A Adduct 0 0 9.0 9~5 9 9 0 0
- Example 7, Part A Adduct 0 0 0 0 0 0 9.5 9.O
Trimethylolpropane 1.0 0.5 1.0 0.5 1.0 1.0 1.0 0.5
~examethoxymethylmel~mine 10 10 10 10 6.7 15 10 10
Phosphoric ac~d 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone Surfact~nt I 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Ethoxyethyl Acetate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Coatin~ Properties
Reverse Impact, in-lbs. 25 50 50 25 25 25 50 75
Acetone '~ubs < - lOC
Pencil Hardness 2H 2H2H 2H 3H H 3H 2H
Adhesion, % ~ 100 -
Thus good overall coating properties were obtained in all
inst~nces. Adhesion was excellent.
~L
A pigmented composition was produced by mixing
90 grams of the prodl~ct of Part A of Example 6, 100 grams
o~ hexamethoxymethylmelamine, 10 grams of the polycapro-
lactone triol used ln Part B of E~am~le 6, 140 grams of
titanium dio~ide, and 40 grams of 2-e~ho~yethyl acetate
and r~lling overnight in a ball mill. A l9-gram portion
of the ~Di~ture was blended with 0.2 gram of stannous
chloride End 1 gram of 2-ethoxyethyl acetate to produce
46.
11855 -C-l
pigmented c~ating compositi~n. A fil~ ~as prepared ~c-
c~rding to the procedure described in ~am~le 1 and cured
for 20 minute.c st 200~F. The film pr~duced was solvent
resist~nt (more than 100 acetone rubs), impact resistan
( re than 320 inch-pounds), and had a 8 pencil hardness.
- amPle 15
-
A ~eries of coat~ng c~mposlti~ns waQ pro~uced
by blending a Qtyrene/ethyl ~crylate/methacrylic acit/
2-hydroxyethyl ~cryl2te Latex compositlon having a total
~olids of 43 weight percent with the product of Part A .
of E~a~ple 6. The aqueous Late~ was dified to imprsve
its fil~-fonming properties a~d to establish that the
~hydride dified ester diol ~lko~ylates ace as a resctive
coalescing ~id. The f~r~lations were produced by mi~ing
the co~onent~ described i~ the followLng table at room
temperature. The pr~duct of Part A of E~ample 6 was ti-
luted t~ 50 weight percent solids with ~istilled water
a~d neutralized to a pH of 7.4 with N,N-dimeehyleeh2nolamine.
Run 1 2 3 4 5 6 7
ComPosition~ solid
Late~c, gms. 10 1~ 10 10 10 10 10
Eacample 6, Part A adduct, gms. 0 0.~ 1.0 1.5 0.5 1.0 0.5
~ex m~thoxyme~hylmelamine O O O 0 0.5 0.5 1.0
Water 13 . 3 13 . 8 14. 3 14 . 8 -13 . 8 14 . 3 13 . 8
F~lms were cast on Bonderite No. 37 s~eel panels
with a No. 60 wi~e-wound rod ~nd allowed to stand under amoient
condition3 overs~ight. ~e ilms were than observed for ap-
pearance and placed in an ov~ for 20 m~nutes at 350 F. The
results are reported ~n the follos~in~ t2ble:
47 O
)7
11855 -C-l
Run l 2 3 4 5 6 7
Film ProPerties
Appearance prior to (1) (l) (2) (3) (4) (3) (3)
curi~g
- Appearance after (l) (1) (2) (3) (4) (3) (3)
cure
Acetone rubs, cycles No cure 60 100 lOO lOO 100 100
Reverse impact, in-lbs. No cure ~3 15 300 ~5 5 4H
~encil hardness No cure ~ F 2B H H 300
___________________O___
(13 Heavy mud cracking
(2) Moderate m~d cracklng
(3) Smooth
(4) Trace of mut cracking
Example 16
Part A - A reactor equipped with a stirrer, condenser,
nitrogen inlet tube and ther~ometer was charged with 100
parts of the ester diol propoxylate of Experinent I and 59
parts o~ phthalic anhydride. The mixture was then hea~ed
to 140C and stirred at this te~perature for 90 ~inutes.
~he anhydride ~odified ester diol propoxvlate adduct was
clear, ~iscous and had an acid num~er of 138 mg~. of KOH/gm.
A 5 gram portion diluted with 15 grams of 2-ethoxyethyl
acetate had a Brookfield viscosity of 460 cps at 27~C (No. 4
spindle, 100 rpm~.
Part B - A series of catalyzed coating co~positions was
produced,applied to steel panels using a No~ 40 ~se wound
rod and cured. ~he for~ulations con~ained 0~1 gran of
Silicone Surfactant I and the following componen~s in gra~s:
48.
11855-C-l
~or~lation A B C D
~art A Adduct 10 10 10 10
Hexamethoxymethylmelamine 4,3 4.8 5.6 0
Epoxide A 0 0 0 10.8
_ - p-ToluenEulfonic Acid 0.05 0.05 0.05 0
Stannous Octoate 0 0 0 0.2
Butyl Acetate 3.1 3.2 3.4 4.9
2-Etho~yethyl Acetate 3.0 3.1 3.3 4.0
Formulations A, B and C were cured at 300~ F
and D at 250F. for 20 minutes. All cured coatings had
reverse and front i~pacts greater than 320 in.-lb. and
10D% crosshatch adhesion values. Fsrmulations A, B and C
passed 100 acetone rubs; formulation D, 65 acetone rubs.
The pencil hardness ~alues of formNlations A, C and D were
2H, that of B was H.
Part C - A second series of formulations was prepared
identical to Formulations A to D but without the addition
of ~ny p toluenesulfonic acid or stannous octoate. These
are identified as Formulations E, F, G and H respec~ively.
In addition Formulation I was produced containing 10 parts
of the Part A Adduct, 0.1 part of Silicone Surfactant I,
7 parts of but~l acetate, 6.3 parts of 2-ethoxyethyl acetate
and 21 parts of bis(3,4-epo~ycyclohexylmethyl) adipate.
The formulations were applied to steel panels as in Par~ B
and cured at 300F for 20 minutes. (Formulations H and I
were also given ~n initial precure of 20 ~inutes at 250F).
All cured coatings had re~erse and front impacts greater
than 320 in.-lb. and 100% crosshatch adhesion values.
Formulations G, H and I passed 100 acetone rubs; for~ulation
49.
2ti~7
11855 - C-l
E, 50 ~cetone rubs; formulation F, 75 acetone rubs. The
pencil hardness values of F, ~ and I were F, that of E was
H and that of H was 3H.
EX _E~
A pigment grind was prepared using 100 parts of
the anhydride modified ester diol ethoxylate of Example
1, Part B, 180 parts of titaniu~ dioxide, 2 parts of
stannous octanoate, 1 part of Silicone Surfactant I, and
4 parts of xylene by grinding in a ball mill.
To 161.5 parts of the pigment grind there were
added 28.9 parts of bis(3,4-epoxycyclohexylmethyl)
adipate, 20.35 parts of 4,4'-dicyclohexy~methane
diisocyanate and 40 parts of xylene and the mixture
thoroughly blended to yield a formulation having a
~iscosity of 180 cps at room temperature. Steel panels
were spray-coated and cured at 220F and 250F to yield
hard, adherent, thermoset coatings with good impact
resistance and high gloss.
Example 18
A series of coating formulations was produced
containing the indicated eomponents. They were then
applied to steel panels using a No. 40 wire-wound rod and
cured at 220~F and 250F for 20 minutes to yield hard,
adherent, thermoset coatings with generally excellent
impact resist~nce. Each formulation contained 10 parts
of the anhydride modified ester diol ethoxylate of
Example 1, Part B, 0.2 part of stannous octanoate, 0.1
part of Silicone Surfac~ant I and 2 parts of 2-ethoxyethyl
acetate in addition to the epoxides identified below.
50.
Z~)7
11855-C-l
Epoxide Isocvanate
. _
Formulation A B A
.
(a~ 3.74 0 4.07
_ (b) 5.78 4.0i
(c) 7.54 0 0.5
(d) Q 11.55 0.5
(e) 11.34 0 0.5
(f) 0 17.3 0 5
Epoxide B - bis(3,4-epoxycyclohexyl-methyl)adipate
lD Isocyanate A - 4,4'-dicvclohexvlmethane diisocyanate
E~a~ple 19
A formulation was proauced by blending 10 parts
of the anhydride m~dified ester diol ethoxylate of Example
1, Part B, 5.78 parts of bis(3,4-epoxycyclohexyl-methvl)
adipate, 4.07 parts of 4,4'-dicyclohexylme~hane diisocyanate
and 0.2 part of stannous octanoate. ~ne mil coatings
were applied to a 0.5 inch ~y 1 inrh portion of two 1 inch
wide by 1.5 inches long ~etal strips. The two coated edges
were held together wnth a paper clip and cured for 20
minutes at 300F. In tw~ replicate tests, it was found that
an avera~e tensile force applied to the two ends of the
adhered strips of about 600 pounds was required to break
the adhesive bond that had been formed.
Esampl~ 20
A series of adhesive compositions was prepared,
ea~h containing 10 parts sf the anhydride ~odified ester
diol ethoxylate of Example 1, Part B, and the ~ollowing
components:
51.
V7
11855-C-l
Adhesive ~ (2)
Epo~ide A O 10
Hexamethoxy~ethvlmelamine 10 0
Stannous octoate 0 0.2
p-Toluenesulfonic Acid 0.2 0
Adhesive (1) required an average tensile ~rce of 8.8
pounds to break the bond; an average tensile force of 37.5
was required with Adhes~-ve (2).
52.
